阅读说明：本技术 一种耐寒型双交联丙烯酸酯橡胶的制备方法 (A kind of preparation method of the double cross-linked acrylate rubbers of hardy type ) 是由 杨兴兵 于 2019-07-16 设计创作，主要内容包括：本发明公开了一种耐寒型双交联丙烯酸酯橡胶的制备方法,包括以下操作步骤：步骤S1、原材料选取；步骤S2、原材料配比；步骤S3、助剂配制；步骤S4、预混；步骤S5、乳液聚合；步骤S6、破乳凝胶；步骤S7、洗胶；步骤S8、烘干、包装,该耐寒型双交联丙烯酸酯橡胶的制备方法,以丙烯酸丁酯、丙烯酸酯乙酯为主要反应单体,并加入Tg点极低的丙烯酸甲氧基乙酯单体改性,采用添加VCA、马来酸以及衣康酸中的一种或两种交联单体,增强丙烯酸酯橡胶的永久压缩变形,Tg可达到-38度,低温脆性可达到-30℃,永久压缩形变低至13％(150度,72h)解决了现有的丙烯酸酯橡胶压缩永久变形大,耐低温差等问题。(The invention discloses a kind of preparation methods of the double cross-linked acrylate rubbers of hardy type, including following operating procedure: step S1, raw material are chosen；Step S2, raw material ratio；Step S3, auxiliary agent is prepared；Step S4, it premixes；Step S5, emulsion polymerization；Step S6, be demulsified gel；Step S7, glue is washed；Step S8, drying, packaging, the preparation method of the double cross-linked acrylate rubbers of the hardy type, with butyl acrylate, ethyl acrylate is main reaction monomers, and it is monomer modified that the extremely low methoxyethyl acrylate of Tg point is added, using addition VCA, one or both of maleic acid and itaconic acid cross-linking monomer, enhance the permanent compression set of acrylic rubber, Tg can reach -38 degree, black brittleness can reach -30 DEG C, permanent compression set is down to 13% (150 degree, it is big 72h) to solve existing acrylic rubber compression set, the problems such as low temperature resistant difference.)

1. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type, which is characterized in that including following operating procedure: step S1, raw material are chosen；Step S2, raw material ratio；

Step S3, auxiliary agent is prepared；Step S4, it premixes；Step S5, emulsion polymerization；Step S6, be demulsified gel；Step S7, glue sulphur is washed Change；Step S8, drying, packaging；

Step S1: raw material main monomer is chosen are as follows: butyl acrylate and ethyl acrylate and methoxyethyl acrylate, propylene Sour n-octyl is one or two kinds of, and cross-linking monomer is chosen are as follows: one of acrylic acid, maleic acid, itaconic acid are compounded with VCA；

Step S2: methoxyethyl acrylate is 55%~60% with n-octyl match ratio, butyl acrylate and propylene Acetoacetic ester match ratio is 45%~55%, and cross-linking monomer accounting is 1%~6%；

Step S3: emulsifier, initiator and molecular weight regulator are equipped with；

Step S4: the step S3 emulsifier being equipped with being added into raw material, is emulsified to raw material, and emulsifying temperature is 32~35 DEG C, emulsification times are 46~60min, obtain raw emulsion；

Step S5: will be added initiator in the obtained raw emulsion of step S4, emulsion polymerization be carried out, under the conditions of 45~85 DEG C Initiated polymerization, then maintaining reaction temperature carries out polymerization reaction at 75~80 DEG C, reacts 2~4 hours, obtains acrylic acid Ester lotion；

Step S6: acrylic acid, maleic acid, itaconic acid are added into acrylic acid ester emulsion and compounds, and it is stirred mixed with VCA It closes, obtains double Crosslinkable Acrylic Polymer Emulsions, the sodium chloride solution that mass percent is 6~7% will be added in obtained lotion, Demulsification gel is carried out under the conditions of 55~60 DEG C；

Step S7: washing the gel after demulsification, and washing temperature is 52 DEG C~80 DEG C obtained rubber compounds, and will be obtained mixed Refining glue, which is put into purl machine vulcanizer, to be vulcanized；

Step S8: at a temperature of being placed on 80 DEG C~110 DEG C to the gel after cleaning, being dried, to obtained after the completion of drying Double cross-linking type acrylic rubber packed.

2. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 1, which is characterized in that institute State the match ratio of raw material in step S2 are as follows: the methoxyethyl acrylate and n-octyl, the total match ratio of Zhan 45.35%, the butyl acrylate and ethyl acrylate, the 53.35% of the total match ratio of Zhan, the cross-linking monomer, Zhan is always matched 1.30%.

3. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 1, which is characterized in that institute It states emulsifier described in step S3 to be formulated by dodecyl oxygen acid sodium and alkyl oxy diphenyl sulfonic acid disodium, wherein dodecane The weight ratio of base oxygen acid sodium and alkyl oxy diphenyl sulfonic acid disodium is (3~4): 1, the initiator is by azodiisobutyronitrile and mistake Ammonium sulfate is formulated, and wherein the weight ratio of azodiisobutyronitrile and ammonium persulfate is (4~6): 1, the molecular weight regulator For one of DDM dodecyl mercaptan and dithiodiisopropyl xanthate, match ratio is 1.2 ‰.

4. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 1, which is characterized in that institute It states and emulsifier is added into raw material in step S4, raw material is emulsified, emulsifying temperature is 35 DEG C, emulsification times 50min, Obtain raw emulsion.

5. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 1, which is characterized in that institute It states in step S5 and initiator is added in obtained raw emulsion, then initiated polymerization under the conditions of 80 DEG C maintains reaction Temperature carries out polymerization reaction at 85 DEG C, reacts 4 hours, obtains acrylic acid ester emulsion.

6. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 1, which is characterized in that institute The sodium chloride solution for being added that mass percent is 7% in double cross acrylate lotion obtained in step S6 is stated, in 60 DEG C of items It is demulsified under part, obtained solid is washed, is dehydrated, after drying, and double cross-linking type acrylic rubber are made.

7. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 6, which is characterized in that institute The match ratio for stating the cross-linking monomer in step S2 is respectively as follows: the acrylic acid Zhan is always matched 0.36%, and the VCA Zhan is always matched 0.84%.

8. a kind of preparation method of the double cross-linked acrylate rubbers of hardy type according to claim 1, which is characterized in that institute Stating curing temperature in step S7 is 160-180 DEG C, and double cross-linked acrylate rubbers are made.

Technical field

The present invention relates to technical field of rubber production, the preparation side of the double cross-linked acrylate rubbers of especially a kind of hardy type Method.

Background technique

It using acrylate is principal monomer by elastomer made of copolymerization that acrylic rubber, which is a kind of, with it is heat-resisting, The advantages that ageing-resistant, oil resistant, uvioresistant, has been widely used for the hydraulic oil transportation of automobile and locomotive in developed countries such as America and Europes The positions such as pipe, cylinder liner, valve rod, crankshaft can be obviously improved the driving condition of automobile, reduce failure and pollution, protection environment And extend automotive service life, therefore enjoy the laudatory title for having " automobile glue ".Currently, acrylic rubber can pass through polymerisation in solution It is prepared with emulsion polymerization, the latter is widely adopted due to having many advantages, such as environmentally friendly, the saving energy.Traditional acrylate Mostly using ethyl acrylate as principal monomer, heat-resisting quantity is had excellent performance rubber clone, can achieve 180 DEG C, the disadvantage is that cold-resistant Property is poor, in addition, the more difficult vulcanization of acrylic rubber, relatively low so as to cause its crosslink density, mechanical property is poor.And nothing Machine filler in acrylic rubber whether it is evenly dispersed also can largely influence its mechanical property, in consideration of it, for upper Problem further investigation is stated, there is this case generation then.

Summary of the invention

The purpose of the present invention is to solve the above problems, devise a kind of system of double cross-linked acrylate rubbers of hardy type Preparation Method solves the more difficult vulcanization of existing acrylic rubber, relatively low so as to cause its crosslink density, mechanical property compared with Difference, and inorganic filler in acrylic rubber whether it is evenly dispersed also can largely influence its mechanical property, and it is cold-resistant The poor problem of property.

Realize above-mentioned purpose the technical solution of the present invention is as follows: a kind of double cross-linked acrylate rubbers of hardy type preparation side Method, including following operating procedure: step S1, raw material are chosen；Step S2, raw material ratio；Step S3, auxiliary agent is prepared；Step S4, premix；Step S5, emulsion polymerization；Step S6, be demulsified gel；Step S7, glue is washed；Step S8, drying, packaging；

Step S1: raw material main monomer is chosen are as follows: butyl acrylate and ethyl acrylate and methoxyethyl acrylate, One of n-octyl or two kinds, cross-linking monomer are chosen are as follows: one of acrylic acid, maleic acid, itaconic acid and VCA Compounding；

Step S2: methoxyethyl acrylate and n-octyl match ratio are 55%~60%, butyl acrylate with Ethyl acrylate match ratio is 45%~55%, and cross-linking monomer accounting is 2%~6%；

Step S3: emulsifier, initiator and molecular weight regulator are equipped with；

Step S4: the step S3 emulsifier being equipped with being added into raw material, is emulsified to raw material, emulsifying temperature be 32~ 35 DEG C, emulsification times are 46~60min, obtain raw emulsion；

Step S5: will be added initiator in the obtained raw emulsion of step S4, emulsion polymerization be carried out, in 45~85 DEG C of items Initiated polymerization under part, then maintaining reaction temperature carries out polymerization reaction at 75~80 DEG C, reacts 2~4 hours, obtains third Olefin(e) acid ester lotion；

Step S6: it is multiple with VCA that one or both of acrylic acid, maleic acid, itaconic acid are added into acrylic acid ester emulsion Match, and be stirred mixing to it, obtain double Crosslinkable Acrylic Polymer Emulsions, is by mass percent is added in obtained lotion 6~7% sodium chloride solution carries out demulsification gel under the conditions of 55~60 DEG C；

Step S7: washing the gel after demulsification, and washing temperature is 52 DEG C~80 DEG C obtained rubber compounds, and will be made Rubber compound be put into purl machine vulcanizer and vulcanized；

Step S8: at a temperature of being placed on 80 DEG C~110 DEG C to the gel after cleaning, being dried, right after the completion of drying Double cross-linking type acrylic rubber obtained are packed.

Preferably, in the step S2 raw material match ratio are as follows: the methoxyethyl acrylate and n-octyl, The 45.35% of the total match ratio of Zhan, the butyl acrylate and ethyl acrylate, the 53.35% of the total match ratio of Zhan, the crosslinking is single Body, Zhan always match 1.30%.

Preferably, emulsifier described in the step S3 is matched by dodecyl oxygen acid sodium and alkyl oxy diphenyl sulfonic acid disodium It makes, wherein the weight ratio of dodecyl oxygen acid sodium and alkyl oxy diphenyl sulfonic acid disodium is (3~4): 1, the initiator It is formulated by azodiisobutyronitrile and ammonium persulfate, wherein the weight ratio of azodiisobutyronitrile and ammonium persulfate is (4~6): 1, the molecular weight regulator is one of DDM dodecyl mercaptan and dithiodiisopropyl xanthate, and match ratio is 1.2‰。

Preferably, emulsifier is added into raw material in the step S4, raw material is emulsified, emulsifying temperature 35 DEG C, emulsification times 50min obtains raw emulsion.

Preferably, initiator is added in obtained raw emulsion in the step S5, causes polymerization under the conditions of 80 DEG C Reaction, then maintaining reaction temperature carries out polymerization reaction at 85 DEG C, reacts 4 hours, obtains acrylic acid ester emulsion.

Preferably, the chlorine that mass percent is 7% is added in double cross acrylate lotion obtained in the step S6 Change sodium solution, be demulsified under the conditions of 60 DEG C, obtained solid is washed, is dehydrated, after drying, and double crosslinking acrylates are made Rubber.

Preferably, the match ratio of the cross-linking monomer in the step S2 is respectively as follows: what the acrylic acid Zhan was always matched 0.36%, the VCA Zhan always match 0.84%.

Preferably, curing temperature is 160-180 DEG C in step S7 described in the step S7, and double cross acrylate rubber is made Glue.

Utilize the preparation method of the double cross-linked acrylate rubbers of the hardy type of technical solution of the present invention production, the hardy type Tg is added with butyl acrylate, ethyl acrylate for main reaction monomers in the preparation method of double cross-linked acrylate rubbers The extremely low methoxyethyl acrylate of point is monomer modified, is handed over using one or both of addition VCA, maleic acid and itaconic acid Receipts or other documents in duplicate body enhances the permanent compression set of acrylic rubber, and Tg can reach -38 degree, and black brittleness can reach -30 DEG C, permanently Big, low temperature resistant difference etc. that compressive deformation down to 13% (150 degree, 72h) solves existing acrylic rubber compression set Problem.

Specific embodiment

The present invention is specifically described below, a kind of preparation method of the double cross-linked acrylate rubbers of hardy type, including Following operating procedure: step S1, raw material are chosen；Step S2, raw material ratio；Step S3, auxiliary agent is prepared；Step S4, it premixes； Step S5, emulsion polymerization；Step S6, be demulsified gel；Step S7, glue is washed；Step S8, drying, packaging；Step S1: former material is chosen Expect main monomer are as follows: butyl acrylate and one of ethyl acrylate and methoxyethyl acrylate, n-octyl or Two kinds of person, cross-linking monomer is chosen are as follows: one of acrylic acid, maleic acid, itaconic acid are compounded with VCA；Step S2: acrylic acid methoxy Base ethyl ester and n-octyl match ratio are 55%~60%, butyl acrylate and ethyl acrylate match ratio be 45%~ 55%, cross-linking monomer accounting is 2%~6%；Step S3: emulsifier, initiator and molecular weight regulator are equipped with；Step S4: The step S3 emulsifier being equipped with is added into raw material, raw material is emulsified, emulsifying temperature is 32~35 DEG C, and emulsification times are 46~60min obtains raw emulsion；Step S5: will be added initiator in the obtained raw emulsion of step S4, it is poly- to carry out lotion It closes, initiated polymerization under the conditions of 45~85 DEG C, then maintaining reaction temperature carries out polymerization reaction at 75~80 DEG C, reaction 2~4 hours, obtain acrylic acid ester emulsion；Step S6: acrylic acid, maleic acid are added into acrylic acid ester emulsion, in itaconic acid One or two are compounded with VCA, and mixing is stirred to it, obtain double Crosslinkable Acrylic Polymer Emulsions, the lotion that will be obtained The middle sodium chloride solution that mass percent is added and is 6~7%, carries out demulsification gel under the conditions of 55~60 DEG C；Step S7: to broken Gel after cream is washed, and washing temperature is 52 DEG C~80 DEG C obtained rubber compounds, and rubber compound obtained is put into purl machine Vulcanized in vulcanizer；Step S8: at a temperature of being placed on 80 DEG C~110 DEG C to the gel after cleaning, being dried, drying Double cross-linking type acrylic rubber obtained are packed after the completion, the match ratio of raw material in the step S2 are as follows: described third Olefin(e) acid methoxy acrylate and n-octyl, the 45.35% of the total match ratio of Zhan, the butyl acrylate and ethyl acrylate, The 53.35% of the total match ratio of Zhan, the cross-linking monomer, Zhan always match 1.30%, emulsifier described in the step S3 is by ten Dialkyl group oxygen acid sodium and alkyl oxy diphenyl sulfonic acid disodium are formulated, wherein dodecyl oxygen acid sodium and alkyl oxy hexichol sulphur The weight ratio of acid disodium is (3~4): 1, the initiator is formulated by azodiisobutyronitrile and ammonium persulfate, wherein azo The weight ratio of bis-isobutyronitrile and ammonium persulfate is (4~6): 1, the molecular weight regulator is DDM dodecyl mercaptan and curing two One of isopropyl xanthan acid esters, match ratio are 1.2 ‰, emulsifier are added into raw material in the step S4, to raw material It is emulsified, emulsifying temperature is 35 DEG C, emulsification times 50min, obtains raw emulsion, obtained raw material in the step S5 Initiator is added in lotion, initiated polymerization under the conditions of 80 DEG C, then maintaining reaction temperature carries out polymerizeing at 85 DEG C anti- It answers, reacts 4 hours, obtain acrylic acid ester emulsion, quality is added in double cross acrylate lotion obtained in the step S6 The sodium chloride solution that percentage is 7%, is demulsified under the conditions of 60 DEG C, and obtained solid is washed, is dehydrated, after drying, is made Double cross-linking type acrylic rubber, the match ratio of the cross-linking monomer in the step S2 are respectively as follows: the acrylic acid Zhan and always match 0.42%, the maleic acid Zhan always match 0.26%, the itaconic acid Zhan always match 0.32%, sulphur in the step S7 Changing temperature is 160-180 DEG C, and double cross-linked acrylate rubbers are made.

The characteristics of the present embodiment is, including following operating procedure: step S1, raw material are chosen；Step S2, raw material are matched Than；Step S3, auxiliary agent is prepared；Step S4, it premixes；Step S5, emulsion polymerization；Step S6, be demulsified gel；Step S7, glue sulphur is washed Change；Step S8, drying, packaging；Step S1: raw material main monomer is chosen are as follows: butyl acrylate and ethyl acrylate and propylene One of sour methoxy acrylate, n-octyl or two kinds, cross-linking monomer are chosen are as follows: acrylic acid, maleic acid, itaconic acid It is compounded with VCA；Step S2: methoxyethyl acrylate is 55%~60% with n-octyl match ratio, butyl acrylate It is 45%~55% with ethyl acrylate match ratio, cross-linking monomer accounting is 2%~6%；Step S3: it is equipped with emulsifier, causes Agent and molecular weight regulator；Step S4: the step S3 emulsifier being equipped with being added into raw material, is emulsified to raw material, cream Changing temperature is 32~35 DEG C, and emulsification times are 46~60min, obtains raw emulsion；Step S5: by the obtained raw material of step S4 Initiator is added in lotion, carries out emulsion polymerization, initiated polymerization under the conditions of 45~85 DEG C, then maintaining reaction temperature exists Polymerization reaction is carried out at 75~80 DEG C, is reacted 2~4 hours, is obtained acrylic acid ester emulsion；Step S6: into acrylic acid ester emulsion One or both of addition acrylic acid, maleic acid, itaconic acid are compounded with VCA, and mixing is stirred to it, obtain double cross connection The sodium chloride solution that mass percent is 6~7% will be added, in 55~60 DEG C of items in type acrylic acid ester emulsion in obtained lotion Demulsification gel is carried out under part；Step S7: washing the gel after demulsification, and washing temperature is 52 DEG C~80 DEG C and mixing is made Glue, and rubber compound obtained is put into purl machine vulcanizer and is vulcanized；Step S8: 80 DEG C are placed on to the gel after cleaning It at a temperature of~110 DEG C, is dried, double cross-linking type acrylic rubber obtained is packed after the completion of drying；This is resistance to The preparation method of the cold double cross-linked acrylate rubbers of type, with butyl acrylate, ethyl acrylate for main reaction monomers, and adds It is modified to enter the extremely low methoxyethyl acrylate of Tg point or methoxyethyl methylmethacrylate monomer, using addition VCA, maleic acid and One or both of itaconic acid cross-linking monomer enhances the permanent compression set of acrylic rubber, and Tg can reach -38 degree, low Warm brittleness can reach -30 DEG C, and permanent compression set solves existing acrylic rubber compression down to 13% (150 degree, 72h) The problems such as permanent deformation is big, low temperature resistant difference.

1, hardy type double cross acrylate rubber system is standby